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By Gilbert Santoro

In this study tantalum carbide filaments of various compositions in the fcc region were prepared by heating a tantalum wire in a measured amount of hydrocarbon vapor. Such properties as tensile strength, transverse-rupture strength, microhard-ness, lattice parameter, electrical resistivity, and magnetic susceptibility were measured as a function of carbon content. Some of these properties showed a maximum or a minimum between a carbon-to-tantalum molar ratio of 0.80 and 0.85, the composition range at which the color changes from metallic gray to gold. The recent literature has shown that in the large homogeneity range for the fcc phase of the Ta-C system there is a marked variation for such properties as microhardness,' electrical resistivity, ' thermodynamic properties,z'3 lattice parameter and superconductivity. In addition to the technological interest of these variations within a single phase, important theoretical benefits may ensue from a continuous investigation of properties vs stoichiometry in tantalum carbide and other refractory defect compounds, for example the effect of the metal-metal distance and crystal structure upon bond formation and electronic structure. Whether there is a similar variation of the tensile strength is of practical importance. Of theoretical interest would be the knowledge of how the magnetic susceptibility varies with carbon composition. Both of these properties, as well as the transverse-rupture strength, were determined for tantalum carbide filaments in the fcc phase region. The lattice parameter, the electrical resistivity, and the microhardness were also investigated and compared with values appearing in the literature. EXPERIMENTAL PROCEDURE Material Preparation. Tantalum carbide specimens of various carbon content were prepared by statically carburizing high-purity tantalum filaments in measured quantities of pure hydrocarbon gas. The filaments, which were 10 mil in diameter and 20 or 40 cm long, were heated by their own resistance at temperatures from 1800" to 2200°C using alternating current in some cases and direct current in others. Tantalum wire from two sources was used. One had a reported purity of 99.96 wt pct Ta. The ingot from which this wire was drawn had been electron beam-melted as the final step in its purification. The reported purity of the other wire, which was prepared by a powder metallurgical process, was 99.88 wt pct Ta. The impurities of both tantalum sources are listed in Table I. Spec-trographic-grade toluene or research-grade propane was used as the source of carbon. The apparatus for the carburization of the filaments is shown schematically in Fig. 1. The system was evacuated to 1 x l0-' mm of Hg when using the electron beam-melted tantalum and to less than 1 p when using the less-pure tantalum. Neither the difference in the base vacuum, nor in the hydrocarbon gas, nor in the tantalum filaments resulted in any detectable difference in the properties studied in this work. However, only the carbides prepared from the higher-purity tantalum were used in the magnetic-susceptibility determinations. Once the base vacuum had been reached, the system was flushed with the hydrocarbon and re-evacuated. For any desired composition of the carbide, hydrocarbon gas was allowed to leak into a constant-volume flask to a predetermined pressure. These pressures were measured by a Cartesian diver-type mercury gage with a range from 0 to 20 mm and with a scale expanded to nine times. The hydrocarbon gas was allowed into the reaction tube and the filament was quickly raised to the reaction temperature. The slack in the filament due to thermal expansion was taken up by drawing out the movable electrode with a screw mechanism. The filaments were kept at temperature from a few minutes to 200 hr. In the majority of cases the heating time was 6 hr. The reaction tube was cooled by cascading water on its outer surface. By means of an ammeter and a voltmeter the electrical resistance at the reaction

Jan 1, 1963

By P. G. Shewmon, W. M. Robertson

The derivative of the surface tension with orientation, ??/??, for copper has been measured over the entire unit triangle. This derivative or torque term was determined from the variation of the dihedral angles at the intersection of twin boundaries and free surfaces. High-temperature anneals in graphite with a hydrogen atmosphere gave torque terms of 0.097 at (111), 0.066 at (100), and 0.0257 at (110). A variation from -36oto +23oC in the dew Point of the H2 had no effect on these values, nor did a change from 99.98 to 99.999 pct Pure copper. The removal of graphite from the system decreased ??/?? slightly. Considering the surface near a low-index plane to be smooth except for occasional steps, the free-energy increment per cm of step is calculated, and it is shown that the observed variation of ??/?? is consistent with a random distribution of steps and an interaction energy between steps. Integration of ??/?? gave the relative values of y at (100), (110), and (111) as comPared to ymax: (Y111/Ymax) =0.974, (Y110/Ymax) =0.996, (y100/Ymax) = 0.983. The ratio of the surface tension of coherent twin boundaries to the surface tension of the free surface was found to be (yT/ys) = 0.027 * 0.011. In a crystalline solid the surface tension y (surface free energy per unit area) depends on the orientation of the surface relative to the crystallographic axes of the crystal. Measurements of this variation of y with surface orientation have been reported for metals only within the last few years. Consider the grain boundary groove shown in Fig. 1. Here the three surfaces are all normal to the plane of the paper, and each has a different surface tension, y1, y2, and y3. If the system is at equilibrium, the total surface free energy must remain unchanged for a slight vertical displacement of the intersection (points A, B, and C are kept fixed). As shown by Herring,' the following equation is obtained:

Jan 1, 1962

By C. A. Bruch, W. E. McHugh, R. W. Hockenbury

EXPERIMENTAL results of the last decade have shown that both accelerator particles and reactor radiations produce significant changes in the properties of metals. These changes, called radiation damage, are important from both academic and engineering viewpoints. An understanding of the radiation damage produced by reactor radiations is difficult, because many kinds of particles having varying energies are present. Therefore, many fundamental studies are being conducted using accelerators in order to obtain nearly mono-energetic beams of various charged particles. Furthermore, many of these experiments are conducted at low temperatures in order to freeze in the radiation-produced lattice defects, after which the specimens are annealed to study the movement of the defects. It is found that although much of the low temperature radiation damage disappears by annealing at room temperature, a significant amount remains. Because there is no assurance that irradiation followed by annealing at a higher temperature will produce the same effect as irradiation at the higher temperature, and because there is an immediate interest in reactor radiation effects during exposures at and above room temperature, a major program is in progress at this laboratory to investigate some of these effects. This paper, representing a part of the program, compares the radiation damage to a group of metals which were exposed under nearly identical irradiation conditions. The metals, representing the three major crystal systems, include copper, nickel, titanium, zirconium, iron, molybdenum, and type 347 stainless steel. The effects of reactor radiations have been treated from a theoretical viewpoint by Seitz' and Ozeroff.' The problem considered by them has been the atomic displacements produced in an infinite medium by mono-energetic beams of both neutrons and charged particles. For reactor experiments, this treatment is not wide enough in scope, because specimens and reactor components are finite, and there are continuous energy spectra of the various particles. Therefore, the theoretical considerations will be extended in this paper to cover reactor conditions and the findings will be compared with the observed radiation damage. Experimental Materials—The six basic metals for this investigation were of commercial or higher purity, and the type 347 stainless steel was of commercial quality. These materials were supplied in various forms ranging from ingots to finished rods, and were fabricated to rods approximately % in. in diam and annealed for specimen stock. A summary of data pertinent to these materials is shown in Table I. The values for chemical compositions include both actual analytical values and typical values supplied by the manufacturer. More information concerning typical

Jan 1, 1957

By F. H. Buttner, E. R. Funk, H. Udin

A. P. Greenough (University College, swansea, Great Britain)—I have recently made some experiments on the deformation of silver wire at high temperature in an atmosphere of oxygen-free nitrogen. The observa-tions which 1 made confirm the main conclusion of this paper, that the most satisfactory mechanism so far suggested to explain the deformation which takes place

Jan 1, 1953

By R. D. Fisher, A. G. Metcalfe, F. A. Crossley

AN investigation of the application of magnetic stirring to the consumable arc melting of aluminum and nickel demonstrated that grain refinement could be obtained when there was sufficient stirring force. Also, it was found that grain refinement could be obtained in aluminum by alternately reversing the polarity of the current through the magnetic stirring coil. The effect of the latter was to periodically reverse the direction of rotation of the molten metal.' Because of their promise, these findings were applied to conventionally cast aluminum. Shortly after this work was begun, Kondic2 reported experiments in which aluminum cast with 40° C (72° F) of superheat exhibited a grain size of 10 to 20 grains per cm2. When interrupted rotation was applied during solidification by mechanical means, a grain size of 800 to 1000 grains per cm2 was obtained. Magnetic Stirring Applied to Conventional Casting— The applicability of magnetic stirring to producing grain refinement in conventionally cast metal was evaluated in the following way. Three pounds of aluminum were cast into a clay-bonded graphite mold. The mold was surrounded by a magnetic stirring coil of 1000 turns. A direct current of 200 amp was passed through the casting by means of a graphite electrode which was immersed from the top. A current of 5 amp was passed through the stirring coil. The aluminum (1100 or 25) was superheated to 1600° F (871° C) and fluxed by passing chlorine gas through the melt for 2 min prior to casting. Two additional castings were made for comparison: 1) a conventional casting of metal superheated to 1600° F and 2) a similar casting through which 200-amp current was passed during solidification, but without current in the magnetic coil. Macrosections of these three ingots are shown in Fig. 1. Very remarkable grain refinement resulted in the magnetically stirred casting. It may be noted that the casting through which 200-amp current was passed has a coarser structure than the conventional casting. It would appear that this is due to the additional heat input generated by the current to the former casting. Mechanical Rotation Applied to Conventional Casting—A casting temperature of 1600° F was used throughout. Some 1 1/2 -lb castings rotated at 150 rpm were predominantly columnar with small areas of coarse, equiaxed grains close to the lower mold wall. Following these, a series of 3-lb castings was made. Macrosections of these ingots are shown in Fig. 2. The imposed rotational speed was 250 rpm. Turbulence or acceleration in the solidifying liquid was the significant factor. Fine grain size resulted in the material solidified during the period of acceleration of the liquid to the imposed rotational speed. When uniform rotational motion was achieved, the grain structure reverted to columnar. The final casting shown in the lower right-

Jan 1, 1962

By E. J. Dulis, A. Kasak, R. C. Westgren

The potential of uirought tungsten- and tantaluw-rich alloys of the W-Ta-Mo-Cb system was investigated for high-strength structural applications above 2500° F. Appreciable strengthening of tung-sten and tantalum—essentially attributable to solid-solzction effects—was obtained with binary, ternary, and quaternary alloys. Tensile strengths as high as 67,000 psi were achieved at 3000 OF. ThE quest for wrought structural materials which possess good strength properties at temperatures above 2000°F has led to a considerable research effort during the past decade. In addition to exploring the potential of various high-melting-point refractory metals (such as molybdenum, columbium, tantalum, and tungsten) for very high-temperature structural applications, alloy-development programs have been undertaken to achieve greater strengths than could be achieved with unalloyed refractory metals. The methods of strengthening refractory metal alloys have included both solid-solution and dispersion strengthening. General relationships among the relevant properties (melting point, recrystallization temperature, and high-temperature strength) of refractory metals indicate that the highest strengths at temperatures of 2500°F or higher would be obtained with tungsten-or tantalum-base alloys. Therefore, the present investigation was undertaken to determine the high-temperature strength potential of solid-solution strengthened alloys based on the binary system W-Ta; to effect further strengthening, minor additions of molybdenum and columbium (at the 6 and 12 pct levels) were made. The portion of the W-Ta-Mo-Cb quaternary alloy system of interest is shown schematically in Fig. 1. The component metals—W, Ta, Mo, and Cb—have a bcc structure at all temperatures, and their binary systems are mutually completely soluble.' Complete solid solubility in the W-Ta-Mo and W-Ta-Cb alloy systems has been demonstrated,' and, therefore, it was expected that the quarternary alloys of the system would also exhibit complete solid solubility at all temperatures. In the virtual absence of contamination by interstitial elements, all the alloys would be truly solid-solution strengthened. Twenty specific compositions of this investigation included binary, ternary, and quaternary alloys of the W-Ta-Mo-Cb system as well as unalloyed tungsten and tantalum. The compositions are shown in Table I. EXPERIMENTAL PROCEDURE Consumable-electrode vacuum-arc melting with ac power was used to produce small laboratory-sized, cylindrically shaped ingots (1-1/4 in. in diameter and 2 to 3-1/2 in. long) of the twenty compositions. A furnace was specially constructed to melt as many as four electrode rods simultaneously into molds lined with tungsten or tantalum sheet. High-purity rods of tungsten, tantalum, molybdenum, and columbium were used for consumable electrodes; the diameter of each rod was determined by the desired weight percentage of the component metal in a given alloy. The details of the construction and operation of the melting furnace will be discussed in another p~blication.

Jan 1, 1964

By Robert E. Green, Kenneth Reifsnider

A microscopic X-ray diffraction technique was employed for the simultaneous study of the behavior of several families of lattice planes, whose local orientatiotz changes are manufestations of internal distortions resulting from specimen deformation. Photographs taken using aluminum were single crystals 1/64 in. In diam are presented which illustrate the appearance of various types of deformation- or growth- induced structural variations. Slip and lattice bending were detected in tensile tests for strains as small as 0.1 pct. Evidence of deformation bands, lineage structure, and void formation wns also shown. AmONG the most important methods of studying internal stresses in metals is the utilization of various X-ray techniques. The general subject of X-ray metallography has been treated in a most excellent manner by Taylor,1 and the use of X-rays for the direct observation of imperfections in crystals has recently been reviewed in an article by Newkirk2 and in the book edited by Newkirk and Wernick.3 Since the inception of metallographic X-ray analysis, there have been numerous technological developments and refinements, each with its particular advantages and disadvantages and, acrording to these, its particular applications. X-ray diffraction techniques can be divided into two general categories, that of X-ray diffraction microscopy and that of X-ray diffraction macroscopy. In the former are included such methods as those of Berg-Barrett, Lang, and Schultz2,3 which are concerned with microscopic imperfections such as dislocations. The second category includes all work concerned with the study of the condition of a crystal lattice structure as indicated by the marroscopic detail in its diffraction patterns. An example of this is the study of the diffraction manifestations of inhomogeneous plastic deformation as manifested by formation of deformation bands and inhomogeneous lattice rotations. The method used in the present investigation was an X-ray diffraction macroscopy technique. The geometry and analytical aspects of the method were similar to those of Julien and Cullity.4,5 The source was collimated with a single slit in a manner simi- lar to the "parallel beam'' method of Barth and Hosemann6 except that a continuous spectrum of radiation was employed. The apparatus produced large-beam transmission Laue patterns of thin cylindrical aluminum-wire crystals, which were deformed either in tension or torsion. Although the conventional X-ray target and interposed slit were not capable of the high resolution obtainable with a fine-focus X-ray source as employed in a microfocus apparatus, resolution was a secondary consideration in our technique, and was sacrificed to obtain sufficient intensity along a sizable length of the specimen. By using a grid indexing technique similar to that of Barth,7 we were able to study several diffraction lines from various planes simultaneously. The results of these tests give additional information with regard to the inhomogeneous deformation of single crystals, and the indexing procedure used provides a correlation between portions of the test specimen and portions of a diffracted beam. EXPERIMENTAL TECHNIQUE The experimental arrangement used is shown schematically in Fig. 1. A source of continuous X radiation from a vertically mounted Machlett X-ray tube possessing a copper target and operated at 20 kv and 10 ma was passed down a horizontal lead tube 80 cm long which terminated in an adjustable vertical brass slit. The slit opening was adjusted to correspond with the diameter of the test specimen. In front of the brass slit it was possible to place a screen wire mesh, one horizontal strand of which was a lead wire which served as a fiduciary mark, the screen itself serving as an indexing system as will be described later. Behind the screen was the test specimen which consisted of an aluminum single crystal wire 1/64 in. in diameter and 3 in. long. These 3-in.-long crystals were cut from

Jan 1, 1965

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By J. A. Berger, R. J. Towner

The pjPocesses of polygonization and subgrain growth were followed in slightly stretched 99.99 pct A1 single crystals heated for cumulative times at 400°, 500°, and 600°C. Changes in sub-grain size and boundary angle were determined from measurements on X-ray micrographs. CAHN1, 2 studied polygonization in stretched and heated aluminum single crystals of 99.99 pct A1 using various techniques, including etch pits, Laue patterns, and a slight restretching of heated specimens to reveal small changes in lattice orientation by the direction of new slip lines. He found that kink bands, which had well-defined boundaries lying in a plane perpendicular to the slip direction (at least in the early stages of deformation), formed during stretching. Also, he noted that bending occurred about the <211> axis lying in the (111) slip plane perpendicular to the <110> slip direction. His studies of polygonization were largely confined to the kink bands rather than to the weakly bent matrix regions between bands. The minimum temperature required to bring about polygonization was established at about 450 "C. Guinier and Tenevin used a focusing Laue X-ray diffraction technique to study polygonization in aluminum single-crystal specimens of 99.99 pct purity. Stretching the crystals 5 pct in tension caused a widening of the focused Laue spots. After heating for 4 hr at 450°C, their method revealed no change in the specimen. Above 450°C polygonization was detected and further annealing near 600°C led to subgrain growth. They concluded that the orientation of the crystal relative to the axis of deformation had no marked effect on polygonization. Gay and Honey-combe4 using an X-ray microbeam technique found that polygonization did not occur in a stretched aluminum crystal heated at 250oC, although some decrease in the yield strength occurred. When the temperature was raised to 475oC, the asterism became broken up as a result of polygonization. Honeycombe5 noted that reflections on X-ray mi-

Jan 1, 1961

By D. Geiselman, A. G. Guy

Single cvystals were grown from high-purity magnesium containing known amounts of nitvogen in the range 0.0008 to 0.0048 wt pet. Crystals of known ovientation were tested in tension in an Instron ma chine to determine the yield strength and to obsevue wheather a yield point occurred. Slowly cooled crystals or those given a solution heat treatment did not show a yield point. However, crystals that were aged following a solution treatment showed a yield point for all of the nitrogen contents studied. It was concluded that nitrogen caused the yield point by the Cottrell mechanism. NITROGEN has been shown to produce sharp yield points in single crystals of cadmium, zinc,2&apos;3 ß-brass,4 and iron,5,6 as well as in polycrystalline iron7 and molybdenum.8,9 Since magnesium has a structure similar to zinc and cadmium, it seemed reasonable that magnesium should also exhibit a sharp yield point provided it contained sufficient nitrogen. Bobalek and Shrader10 reported a total nitrogen content of 0.002 to 0.0065 wt pct in com- mercial magnesium alloys, an amount well in excess of that required by theory. However. magnesium differs from cadmium and zinc in that it forms a stable nitride, Mg3N2, which has a standard free energy of formation of -95,480 cal per mole at 25" c." If rather than being in solid solution, the nitrogen were predominantly combined as the nitride, it could not act to produce a yield point. This type of behavior is the basis for the elimination of strain aging and a yield point in steel by the addition of strong nitride formers such as titanium,12 columbium,13 aluminum,14 vanadium,15 and boron.16,17 Thus, there appeared to be factors both favorable and unfavorable to the production by nitrogen of a sharp yield point in magnesium, and the purpose of this investigation was to determine the actual behavior of magnesium crystals containing known amounts of nitrogen.

Jan 1, 1960

By R. M. Rose, D. P. Ferriss, J. Wulff

The effect of orientation on the stresses, nctivation energies, and activation volumes for yielding and plastic flow of tungsten single crystals was investigated. Tensile tests showed the proportional limit to be a function of orientation: crystals whose tensile axes were near the [I10} direction were roughly three times as strong as [loo] crystals. The [ 1101 crystals showed low strain hardening and displayed yield phenomena, whereas the other orientations yielded smoothly and showed considerable strain hardening. The fracture mode was cleavage, except for crystals near the [1101 , many of which gave "chisel" fractures at 300°and 373°K. The activation energy for yielding was approximately one- half an electron; volt at all orientations, and the volume of activation was (12 to 14)b3, except near the [1101, where it was 7b3. Activation volumes generally increased after yielding. The most common theoretical models for yielding and strain hardening of bcc metals were. found to be insufficient to the intepretation of the observations here in. An explanation is proposed, based on the dislocation reaction dislocation networks and jogs, md jogs formed during plus tic flow. PRECLSE knowledge of the Drocesses involved in the yielding and plastic flow of the refractory metals is essential to the formulation of models for their flow and fracture. Despite this need, the single -crystal investigations, especially of tungsten, have been sparse. Slip occurs at low temperature, according to schadler,i in <111> directions on {110) planes; as the temperature rises to room tempera-

Jan 1, 1962

By W. C. Elli, M. E. Fine

YOUNG&apos;S modulus of elasticity in metals ordinarily decreases with rising temperature. The range of the thermoelastic coefficient at room tem- 1/E dE/dT perature (temperature coefficient of modulus, is illustrated1 by the values for tungsten and hard-drawn aluminum, —95 and —1220x10-6 eg C-1. However, a nearly zero thermoelastic coefficient is observed in some ferromagnetic alloys over a limited temperature range. In these alloys, as the temperature is raised, an increase in modulus arising from loss of ferromagnetism compensates the normal decrease. Iron-nickel alloys containing 36 to 52 pct Ni behave in this manner. In the present investiga- tion, the dependence of the modulus and thermo-elastic coefficient on cold working and annealing were studied in iron-nickel alloys in this range of nickel. Although these alloys, when fully annealed, have a coefficient near zero over a very small temperature interval, the temperature range of low coefficient can be extended greatly by straining and then stress-relief annealing. The modulus of face-centered cubic iron-nickel alloys annealed at 1000°C does not vary linearly with composition at room temperature but, as shown by the solid line of fig. 1, from Koster,&apos; is minimum at 40 pct Ni and maximum at 87 pct Ni. The modulus increases with applied magnetic field but retains the minimum near 40 pct Ni. Schematic change of modulus with temperature for three compositions is shown in fig. 2.&apos;. &apos; With increasing temperature, the slope becomes less negative, goes through zero (temperature of minimum modulus for the alloy), becomes positive, and resumes its normal negative value above the Curie

Jan 1, 1951

By E. H. Rennhack

Phase equilibria of the zinc-rich portion of the Zn-Fe-A1 system containing up to 20.0 wt pct Fe and Al have been investigated at 600°C (1112°F), 450°C (842°F), and room temperature by metallographic and X-ray diffraction techniques. The phase relationships were found to involve only those phases present in the three binary systems. THE presence of small quantities of aluminum (approx. 0.2 wt pct*) in zinc galvanizing baths is known to suppress the formation of Zn-Fe alloy layers within the coating.&apos; As part of an extended investigation of this suppression effect and the alloy reactions involved, the zinc-rich corner of the Zn-Fe-A1 equilibrium system containing up to 20.0 pct Fe and Al was determined at 600°C (1112°F), 450° F (842° F), and room temperature. The present paper reports the findings of this study. The constitution of the Zn-Fe system has been reported by Raynor2 based mainly on the work of Schramm3-3 and Truesdale et a1.6 The solid solubility of iron in zinc is extremely small and lies between 0.0009 and 0.0028 pct in the range 150° to 400°C (302°to752°F). Within the temperature and composition range of interest, a eutectic reaction involving nearly pure zinc, liquid = Zn+FeZn13, is observed at about 419°C (786° F) and 0.018 pct Fe along with a peritectic reaction, FeZn7+ liquid e FeZn13, at 530°C (986° F) and 6.2 pct Fe. The latter reaction is sluggish due to the large proportipn of solid phase involved in the transformation. Halla et al.,7 identified the compound FeZn13 as monoclinic with a = 13.68, b = 7.63, c = 5.07, and B = 128°44&apos;. The structure of FeZn7 was reported by Bablik, et al.,8 to be of hexagonal symmetry, belonging to either the C6v = C6/m mc or D46h = C6/mc space group. Divensions of the unit cell are a = 12.81A and c = 57.6a. The Zn-A1 diagram as composed by Raynor9 and later Gebhardt10 is characterized by a eutectic decomposition, liquid 382°C (720°F) and 95.0 pct Zn and a eutectoid decomposition, at 275° (527°F) and 78.0 pct Zn. The eutectoid reaction cannot be suppressed permanently by quenching. Above 275° (527° F), a and a&apos; co-exist in a closed miscibility gap between 31.6 and 78.0 pct Zn. Both phases are fcc and have nearly the same lattice parameter. The maximum solubility of aluminum in zinc (B) is approximately 1.0 pct at the eutectic temperature. PROCEDURE Materials. The experimental alloys were prepared from both massive and powdered material. Cast alloys were composed from three zinc-base master alloys containing 8.0 pct Fe, 16.0 pct Fe, and 50.0 pct Al which were made from C.P. zinc, Armco iron, and

Jan 1, 1962

By P. Chiotti, G. R. Kilp

Thermal, metallographic, vapor pressure, and X-ray data were obtained to establish the phase diagram for the zinc-zzrconiz~m system. Five compounds corresponding to the stoi-chiometric formulas ZrZn, ZrZn,, ZrZn,, ZrZn,, and ZrZn14 were observed. All these compounds, with the exception of ZrZn2, which melts congruently at 1180°C under constrained zinc-vapor conditions, undergo pexitectic reactians. The temperature at which the zinc vapor pressure is I atm for a series of alloys was determined from vapor-pressure measurements. The data obtained are summarized in the construction of a I-atm-pressure phase diagram and a phase diagram corresponding to a pressure of less than 10 atm. THE purpose of this investigation was to establish the phase diagram for the zinc-zirconium system. Thermal, metallographic, vapor pressure, and X-ray data were employed in determining the phase regions. Partial investigations of this system have been conducted by Gebhardt1 and Carlson and Borders.&apos; Carlson and Borders studied the high-zirconium region and established the existence of a eutectic at 69 wt pct Zr with a melting point of 1015°C. The terminal phases of the eutectic horizontal were shown to be an intermetallic compound ZrZn and a solid solution of ß zirconium containing 21 wt pct Zn. The ß solid solution decomposes into ZrZn and a zirconium at 750°C. The eutectoid composition is given as 15 wt pct Zn, and the solubility of zinc in a zirconium at temperatures below 750°C is indicated to be negligible. Gebhardt studied the zinc-rich region and observed a lowering of the melting point of zinc from 419.5" to 416°C and temperature horizontals at 545" and970°C. Some preliminary observations by Chiotti, Ratliff, and Kilp were reported by Hayes.2 pietrokowsky3 has reported the compound ZrZn2 to have a cubic MgCu2 structure with ao = 7.396A. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc or Baker analyzed reagent granulated zinc, both 99.99 pct pure and hafnium-free iodide-process crystal bar zirconium obtained from the Westinghouse Electric Corp. The zirconium contained 200 ppm Fe, 200 ppm Si, 100 ppm C, and minor amounts of other impurities. The zirconium was milled or machined into thin chips or shavings. These were cleaned with a nitric-hydrofluoric acid solution, rinsed with water, and acetone, and dried just prior to their use in alloy preparation. The granulated zinc was similarly cleaned using dilute nitric or hydrochloric acid. Weighed quantities of these materials, 20 to 30 g total, were mixed and pressed at 20,000 to 70,000 psi to give relatively dense compacts. During the early part of this investigation the pressed compacts were placed in MgO-15 wt pct MgF, crucibles which were then sealed inside of quartz ampules. The compacts were given various prolonged heat treatments prior to their use for thermal analyses, or vapor-pressure measurements. Because of expansion of the compacts and the relatively high zinc vapor pressure it was difficult to heat to the melting temperatures of the alloys without failure of the quartz ampules. Homogenization at temperatures below the melting temperature gave brittle, porous alloys unsuitable for metallographic examination. It was also difficult to prevent condensation and segregation of zinc on the colder parts of the quartz ampules during heating and cooling operations. These problems were eliminated to a great extent by the use of tantalum crucibles. Tantalum proved to be a satisfactory container with little or no reaction between the alloys and the tantalum. Small tantalum thermocouple wells were successfully welded in the bottom of these crucibles. Pressed compacts were sealed inside the tantalum crucibles by welding on preformed caps under an argon atmosphere. Heat treating and differential thermal analysis were combined into a single operation. The experimental sample assembly is shown in Fig. 1. This assembly was enclosed inside a stainless-steel tube heating chamber which could be evacuated and filled with an inert gas. The thermocouple leads were brought out of the heating chamber between two rubber gaskets used to provide a vacuum seal for the water-cooled head. Most of the compounds in this system undergo peritectic decomposition. After heating above the temperature of a particular peritectic horizontal the sample was cooled to just below the peritectic temperature and held at temperature for several hours. The sample was then reheated through the peritectic temperature and the size of the thermal arrest, if still present, compared with the one previously obtained. If the thermal arrest was not characteristic for the alloy composition being investigated its magnitude diminished and repeated cycling and annealing eventually eliminated it. The peritectic thermal arrests characteristic of a particular composition were established in this manner.

Jan 1, 1960

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.&apos; Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo&apos;s results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By R. L. Fullman

Relationships are derived between average dimensions measured on a polished cross section and the spatial dimensions of particles dispersed as uniform cylinders. The equations are applicable to the measurement of rods or plates without the stipulation that they be extremely thin. QUANTITATIVE analysis of the elements of mi-crostructures has been limited by a lack of knowledge concerning the relationships between observations on plane surfaces and the spatial nature of the structure. This paper is an extension of previous efforts to establish equations suitable for the quantitative investigation of microstructures. The equations derived fill two gaps in the range of particle shapes for which measurements may be required, namely those shapes lying between extremely thin plates and equiaxed particles (approximately spherical), and those intermediate between equiaxed particles and extremely thin rods or needles. In a previous paper&apos; equations were developed relating dimensions measured on a polished cross section to the average spatial dimensions of particles in the form of spheres, extremely thin plates, and extremely thin rods. For extremely thin rods the dimensions measured on a polished cross section were found to depend on the radius only, so that no information concerning the rod lengths or number of rods per unit volume could be obtained from observations on a cross section. In this paper equations are derived relating dimensions measured on a polished cross section to the spatial dimensions of particles in the form of identical cylinders. These equations may be used to evaluate the dimensions of rods, as well as the dimensions of plates, without the stipulation that the plates or rods be extremely thin. The impossibility of evaluating the length of extremely thin rods from planar measurements appears as an increase in the amount of data required for a given precision, as the length-radius ratio increases. Consider a sample containing particles of a phase in the form of cylinders of uniform radius T and height t. If the cylinders are randomly oriented, as in a sufficiently large sample of a fine grained poly-crystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the cylinders are not randomly oriented, it is necessary to randomize the orientations of the cross-sectional planes and traverse lines. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of particles N, cut by the cross-sectional plane per unit area is equal to the number of particles N, per unit volume times the probability p1 of a plane intersecting a single randomly positioned and randomly oriented cylinder in the cube. Let J be the maximum cylinder dimension in the direction normal to the cross-section planes, as shown in Fig. 1. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length J

Jan 1, 1954

Jan 1, 1940

Jan 1, 1942

By Charles S. Barrett

There is a road into the microscopic realm that has remained untraveled through all these years of intense activity with high-power optical and electron microscopy. The road is worthy of careful scouting by metallurgists and other investigators, for it leads into relatively new country and it makes some areas accessible that heretofore could be reached only by very indirect paths or by the use of imagination. And when the road passes through familiar territory it frequently permits a new view of commonplace things that should prove of value from time to time. An accepted way to interest people in new sights such as this is to present an illustrated travelogue. This I propose to do, using many pictures taken in my recent exploration of this road. In the manner of travelogues, I shall touch briefly upon a large number of different subjects in physical metallurgy and shall attempt to give an exhaustive treatment of none, for the objective is to provide a means for further research, to interest others in it, and to indicate what appears at the moment to be profitable directions for it to take. The method I shall present involves X-rays, but does not make use of the usual accompaniments of X-ray research such as reciprocal lattices, Fourier series, or the stereographic projection. The method is so simple in its fundamentals that it could have been developed 2o years ago, or perhaps even 30 years ago. It is well to have a destination for our travels, so that when we are through we shall have explored some region of importance, despite our preoccupation with the novel means of transportation and our interest in the sights to be seen along the way. So let us name the Cold-worked State as our destination, and make side trips into the territories known as Recovery, Recrystallization, and Precipitation-hardening. A great many investigations have been made of the nature of cold-worked metal, and a great variety of methods used, many of which are indirect, such as X-ray line intensities, X-ray line widths, calori-metric measurements, and magnetic measurements. Since comprehensive reviews of these investigations have been published in recent years, they need not be discussed here. The investigations that were the direct forerunners of the present work should be first mentioned. In 1931 I became interested in the structure of individual spots in X-ray diffraction patterns.l When a crystal is placed in the narrow pencil of X-rays in a Laue camera, the spots recorded on the film are not always uniformly black, but may have an internal structure. The meaning of this may be understood from Fig. I, which represents a narrow beam containing X-rays of many wave lengths (&apos;&apos;general radiation") penetrating a crystal in the direction of the arrow and forming a pattern on the vertical film at the right.

Jan 1, 1945

Jan 1, 1941